Acetylenization of mineral oils



y 1937- H. 1. WA'i'ERMAN 2,088,500

ACETYLENIZATION OF MINERAL OILS Filed April 20, 1955 Di/uenf Arvmaf/c Hgdmgrbon 0/7;

Acefg/ene 5 4' filudge Eeszhaus or Refined Di/uem Pef/ned Oil Oil Patented July 27, 1937 UNITED STATES PATENT OFFICE ACETYLENIZATION OF MINERAL OILS Hein Israel Waterman, Delft, Netherlands, as-

signor to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application April 20, 1935, Serial No. 17,492 In the Netherlands April 23, 1934 Claims. (01. 196-78) My process relates to the treatment of mineral purposes may form a suitable raw stock for prooils with acetylene in the presence of aluminum ducing my improved hydrocarbon product by chloride or other suitable catalysts. In particular ordinary refining methods. Generally, however, it deals with the treatment of mineral oils con- I continue the treatment by stopping the influx 5 taining aromatics, and with the production of of acetylene and allowing the mass to digest prefvaluable products therefrom. erably in an atmosphere of acetylene, and at a It is a purpose of my invention to provide a moderately elevated temperature, which may be method whereby stocks of relatively low value the temperature of the first treatment. The can be converted into valuable and useful proddigestion period may extend from hour to more ucts. For instance, my method enables the prothan 24 hours, depending upon the treating stock 10 duction of refined smokeless kerosenes, high visand product desired. A secondary product of recosity index lubricating oils, resinous products action is formed from which my improved prodsuitable for paints and varnishes, plastic masses ucts are separated by known means as explained adaptable for moldings, drying oils, etc., from later.

cracked fuels and similar low grade hydrocarbon At times and depending upon the desired end 15 oils. Furthermore, undesirable sulfur compounds products, acetylenization and digestion periods are removed. may be repeated alternately several times. This Suitable treating stocks are crude oils containprocedure may prove especially useful in the ing aromatics such as are found in Borneo and manufacture of resins.

California, or distillates or residues therefrom; During the active treatment'the temperature is cracked products, in particular residues from preferably kept below about 50 C., for example cracking operations; Edeleanu extracts or exbetween about C. and 50 C.; in some special tracts from other solvent extraction processes; instances temperatures of 0 C. or even below liquid products obtained from thermal treatment may be used. For producing high quality proda of hydrocarbons or by hydrogenation of coal or ucts, temperatures above 50 C. should in general 5 other carbonaceousmaterials; as well as coal tar be avoided; in some instances temperatures exproducts. The presence of aromatics in the ceeding 50 C., e. g. up to about 100C may be treating stock is desirable and in general oils conapplied, for example in cases where the productaining less than 20% aromatics respond insuflition of somewhat darker reaction products is not ciently to warrant the expense of the treatment. objectionable.

Depending upon the choice of treating stocks and During the introduction of acetylene the vistreating conditions the predominance of certain cosity of the reaction mass rises and it may beproducts of reaction can be varied at will and come so thick, as to make proper contact with the within wide limits. j gas impossible. In such a case the treating stock Specific applications of the process consist of may be diluted with inert hydrocarbon diluents improving the viscosity index of lubricating oils such as cyclohexane, petroleum ether, kerosene whose low V. I. is due to the presence of arofree of aromatics, etc. Should the diluent conmatics, or of desulfurization. t'ain aromatics, then it will participate in the re- In a. particular instance, the sulfur content of action and contribute to the thickening. 40 a. kerosene was lowered from 1.6% to .3% and The pressure of acetylene can be varied over 40 owing to the removal of aromatics the ring wide ranges as a general rule. Increase of presnumber had risen from 26 to 53. In order to sure accelerates the reaction. This may be dedesulfurize an oil, deficient in aromatics, I may sirable, when using gases which are relatively add aromatics to it, prior to introducing acetypoor in acetylene, such as are obtained by cracklene. Gasoline, kerosene, gas oil, etc., can be d-eing or incomplete combustion of hydrocarbon sulfurized in this manner. gases, or by treatment of hydrocarbons in the In mypreferred procedure I introduce for a electric arc. The acetylene may be applied improlonged period, which may be of the duration mediately after its manufacture, whilst still in of several hours, acetylene or gases containing statu nascendi or at least hot. acetylene into the oil to be treated, which con- The amount of acetylerie absorbed, besides betains aluminum chloride or other polymerizing ing important in the economy of the process, catalyst in suspension. During this time the determines to a large extent the nature of the I liquid-mass is kept agitated to provide for a reaction products. Thus the amount of absorbed thorough cont ct of the reactant. A primary acetylene may vary from less than about 3% to product of reaction is formed, which for some 10% on' the aromatic content of the treating stock 55 in manufacturing processes in which liquid hydrocarbons are the main products, and from 10% to 20%, when resins are formed. As previously pointed out, stocks containing no or only small percentages of aromatics do not respond readily to acetylenization.

My process is further explained in the attached drawing to which I now refer. Hydrocarbon oil to be treated comprising non-aromatic hydrocarbons and normally containing a substantial portion of aromatic hydrocarbons is admitted-to reactor I through line 2 from a source not shown. If the oil should bee deficient in aromatic hydrocarbons, suitable aromatics may be added through line 3. When the reactor 1 is charged to the desired level, catalyst is introduced through line 4 and acetylene through line' 5. Unreacted acetylene or inert gases admixed therewith are vented through line 6 and may be recovered in any suitable manner.

After the reaction has progressed to the desired point, the influx of acetylene is shut off and the reaction mixture is preferably allowed to digest for several hours. Sludge normally containing the spent catalyst settles out and is withdrawn through sludge line I. Sometimes, however, the reaction mass may become too viscous to allow settling of the sludge. In this case a. suitable diluent or precipitant such as liquid propane, petroleum ether, etc., may be added through line 8, which diluent effectively separates sludge and also mayseparate a portion of substantially all of the resinous reaction products. precipitated mass is then withdrawn through sludge line 1. The supernatant liquid, whose content of aromatics and sulfur compounds if sulfur compounds were present, has been greatly reduced, is transferred through line 9 to still Ill.

After completed acetylenization, one of several courses may be followed, depending on the type of oil treated and the type and amount of diluent used. If the treated oil contains material .portions of the high molecular weight reaction products between acetylene, aromatics and sulfur compounds, if sulfur compounds were present,"

the unreacted portion of the oil which consists essentially of non-aromatic hydrocarbons, is taken overhead together with the diluent, high molecular weight compounds remaining in the still as residue, usually in the form of resins. The latter may be withdrawn through line ll while the diluent vapors proceed through vapor line l2 and condenser I3, an unreacted oil may be taken as a side stream through line II and condenser 15. i

If no diluent was used the entire overhead may be conducted through line I4 and condenser I5.

If on the other hand treatment with the diluent was very effective so as to result in the removal of the greater portion of high molecular weight reaction products together with the sludge in reaction vessel I, then distillation may be required only to distill the diluent, and the refined oil may be withdrawn as still bottoms through line H. i

The product of reaction normally consists of a complicated mixture of many substances, lubricating oils, resins and other viscous hydrocarbons which can be refined or separated by distillation and/or treating with sulfuric acid and/or extraction methods. Inasmuch as aliphatic and naphthenic hydrocarbons are not substantially affected by acetylenization as herein described, the present treating method in combination with distillation affords a means for separating them The entire I extracted with benzol.

Example I Lubricating stock with a specific gravity of .9640 having a V. I. of 9 was dissolved in petroleum ether. 13.6% aluminum chloride on the weight of the oil were added and dry acetylene was introduced for 3 hours at C. while v agitating. 2.8% acetylene based on the weight of the oil, or approximately 9% based on the aromatics contained therein, were absorbed. The mixture was allowed to digest for 40 minutes at 50 C. and then for 16 hours at room temperature.

The product of reaction was partly solid. It was extracted with petroleum ether (40-60 C. boiling range). The soluble part was filtered through clay and topped the distillation residue was a lubricating oil amounting to 71.6% of the treating stock and had a good color, a specific gravity of .9338 and a V. I. of 61.

The residue from the first extraction was further extracted with a mixture of benzol and petroleum ether. 12.9% of a brown colored high- 1y viscous mass was recovered after filtering through clay and topping.

- The residue from the second extraction was treated with water to decompose the aluminum chloride and its complex compounds and was 8.4% of brown resins were obtained after separating benzol from the extract.

Example 11 A cycle stock very rich in aromatics and with a boiling range of about 170 to 340 C. and a specific gravity of 0.9833, obtained in the crackifigf of mineral oil-containing aromatics, was

The very viscous reaction mass was extracted with petroleum ether. The extract, after evaporation of the petroleum ether, was subjected to vacuum distillation and yielded a colourless oil boiling between 50 and 150 C. at 1.2 mm. pressure in a quantity of 26.2% of the base'materials, whilst as residue a light brown transparent resin was obtained in a quantity of 7.3% of the base materials.

The residue from the first extraction yielded. on extraction with a mixture of 2 parts petroleum ether and 1 part benzol, an extract from which a light yellow oil fraction boiling between 50 and 140 C. at 1.4 mm. pressure was obtained bycan be increased still further.

While I have found that anhydrous aluminum chloride is the most active catalyst, other catalysts suitable for promoting polymerization reactions can be used as well. To mention a few: boron fluoride, zinc chloride, titanium chloride, ferric chloride, etc. have produced favorable results.

I claim as my invention: a

1. In the process of refining a mineral oil containing aromatic and non-aromatic hydrocarbons to produce a refined product having a substantially lower content of aromatic hydrocarbons, the steps of treating said mineral oil with acetylene in the presence of a polymerization catalyst under conditions to react the acetylene with the aromatic hydrocarbons and to convert at least a portion thereof to compounds of higher molecular weights without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreacted non-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

2. The'process of claim 22 in which said higher molecular weight hydrocarbons and the remaining substantially unreacted oil are separated by distillation.

3. In the process of refining a mineral lubricating oil containing aromatic hydrocarbons of low viscosity index and non-aromatic hydrocarbons of higher viscosity index to produce a, refined lubricating oil of improved viscosity index having a substantially lower content of aromatic hydrocarbons, the steps of treating said mineral lubricating oil with acetylene in the presence of a polymerization catalyst-under conditions to react the acetylene with the aromatic hydrocarbons and to convert at least a portion thereof to resinous compounds of higher molecular weights without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreacted non-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

4. In the process of refining a mineral oil containing aromatic and non-aromatic hydrocarbons and sulfur-bearing compounds to produce a refined product having a substantially lower content of aromatic hydrocarbons and sulfur-bearing compounds, the steps of treating said mineral oil with acetylene in the presence of a; polymerization catalyst under conditions to react the acetylene, sulfur-bearing compounds and aromatic hydrocarbons with each other and to convert at least a portion thereof to compounds of higher molecular weights, without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreactednon-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

5. In the process of'refining a non-aromatic hydrocarbon oil containing sulfur-bearing compounds .to produce a refined product having a substantially lower content of sulfur-bearing compounds, the steps of adding an aromatic hydrocarbon to said oil, treating the resulting mixture with acetylene inthe presence of apolymerization catalyst under conditions to react the acetylene, sulfur-bearing compounds and aromatic hydrocarbons with each other and to convert at least. a portion thereof to compounds of higher molecular weights, without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreacted non-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

HEIN ISRAEL WATERMAN.

CERTIFICATE OF CORRECTION.

Patent No. 2,088, 500.

HEIN ISRAEL wArERnAN.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows Page 5, first column, line 28, claim 2, for the claim reference numeral "22" read '1; and that the said'Letters Patent should be read with .this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 19th day of October, A. D. 1957.

(Seal') Henry VanArsdale. Acting Commissioner of Patents.

can be increased still further.

While I have found that anhydrous aluminum chloride is the most active catalyst, other catalysts suitable for promoting polymerization reactions can be used as well. To mention a few: boron fluoride, zinc chloride, titanium chloride, ferric chloride, etc. have produced favorable results.

I claim as my invention: a

1. In the process of refining a mineral oil containing aromatic and non-aromatic hydrocarbons to produce a refined product having a substantially lower content of aromatic hydrocarbons, the steps of treating said mineral oil with acetylene in the presence of a polymerization catalyst under conditions to react the acetylene with the aromatic hydrocarbons and to convert at least a portion thereof to compounds of higher molecular weights without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreacted non-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

2. The'process of claim 22 in which said higher molecular weight hydrocarbons and the remaining substantially unreacted oil are separated by distillation.

3. In the process of refining a mineral lubricating oil containing aromatic hydrocarbons of low viscosity index and non-aromatic hydrocarbons of higher viscosity index to produce a, refined lubricating oil of improved viscosity index having a substantially lower content of aromatic hydrocarbons, the steps of treating said mineral lubricating oil with acetylene in the presence of a polymerization catalyst-under conditions to react the acetylene with the aromatic hydrocarbons and to convert at least a portion thereof to resinous compounds of higher molecular weights without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreacted non-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

4. In the process of refining a mineral oil containing aromatic and non-aromatic hydrocarbons and sulfur-bearing compounds to produce a refined product having a substantially lower content of aromatic hydrocarbons and sulfur-bearing compounds, the steps of treating said mineral oil with acetylene in the presence of a; polymerization catalyst under conditions to react the acetylene, sulfur-bearing compounds and aromatic hydrocarbons with each other and to convert at least a portion thereof to compounds of higher molecular weights, without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreactednon-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

5. In the process of'refining a non-aromatic hydrocarbon oil containing sulfur-bearing compounds .to produce a refined product having a substantially lower content of sulfur-bearing compounds, the steps of adding an aromatic hydrocarbon to said oil, treating the resulting mixture with acetylene inthe presence of apolymerization catalyst under conditions to react the acetylene, sulfur-bearing compounds and aromatic hydrocarbons with each other and to convert at least. a portion thereof to compounds of higher molecular weights, without substantially changing the constitution of the non-aromatic hydrocarbons, and concentrating the unreacted non-aromatic hydrocarbons by separating said higher molecular weight compounds therefrom.

HEIN ISRAEL WATERMAN.

CERTIFICATE OF CORRECTION.

Patent No. 2,088, 500.

HEIN ISRAEL wArERnAN.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows Page 5, first column, line 28, claim 2, for the claim reference numeral "22" read '1; and that the said'Letters Patent should be read with .this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 19th day of October, A. D. 1957.

(Seal') Henry VanArsdale. Acting Commissioner of Patents. 

